7Li NMR chemical shift titration and theoretical DFT calculation studies: solvent and anion effects on second‐order complexation of 12‐crown‐4 and 1‐aza‐12‐crown‐4 with Lithium cation in several aprotic solvents |
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Authors: | Marilyn C Masiker Charles L Mayne Brian J Boone Anita M Orendt Edward M Eyring |
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Institution: | 1. Department of Chemistry, University of Utah, Salt Lake City, Utah 84112‐0850, USA;2. Center for High Performance Computing, University of Utah, Salt Lake City, Utah 84112‐0190, USA |
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Abstract: | 7Li NMR titration was used to determine stepwise complexation constants for the second‐order complexation of lithium cation with 12‐crown‐4 in acetonitrile, propylene carbonate and a binary mixture of propylene carbonate and dimethyl carbonate. The anions used were perchlorate, hexaflurophosphate and trifluromethanesulfonate. A second ligand 1‐aza‐12‐crown‐4 was similarly investigated. The exchange between the free and complexed cation in these reactions is fast on an NMR timescale resulting in a single lithium peak which is a concentration‐weighted average of the free and bound species. Solvent effects show that the 1:1 complex is much more stable in acetonitrile than in propylene carbonate or in the propylene carbonate dimethyl carbonate mixture. Anion effects for a given solvent were small. Optimized geometries of the free ligands and the 1:1 and 1:2 (sandwich) metal–ligand complexes were predicted by hybrid‐density functional theory using the Gaussian 03 software package. Results were compared to literature values for 1:1 stability constants found by microcalorimetry for several of these systems and are found to be in good agreement. Although microcalorimetry only considered the formation of 1:1 complexes, 7Li NMR shows evidence that both 1:1 and 1:2 complexes should be considered. Copyright © 2009 John Wiley & Sons, Ltd. |
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Keywords: | NMR 7Li 12‐crown‐4 1‐aza‐12‐crown‐4 stability constants complexation DFT calculations |
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